Anti-solar polymers, method of making the same and cosmetic compositions containing the same

ABSTRACT

An anti-solar polymer has in the macromolecular chain thereof at least one unit of the formula ##EQU1## wherein F is a residue derived from an aromatic compound imparting to the polymer the ability to absorb wave lengths of light in the range of about 280-315 millimicrons. The polymer is employed in a cosmetic composition.

The present invention relates to novel "antisolar" polymers which are particularly useful in cosmetic preparations, to the process for preparing these new polymers and to cosmetic compositions containing the same.

Sunburn, or erythema, results from the excessive exposure of human skin to the rays of the sun and the wave lengths of light in the range of 280 to 315 millimicrons, often called the "erythematous zone" are those which produce such sunburn.

Below this wave length range the sun rays do not present any particular danger, for they are filtered by the ozone in the atmosphere.

However, the UV rays which are responsible for or which produce a desirable suntan are those in the zone ranging from 315 to 400 millimicrons.

Consequently, if one desires to be exposed to solar radiation, it is important that the skin be protected with the aid of a composition containing a substance which absorbs the UV rays in the erythematous zone, thereby avoiding an undesirable sunburn, which composition however also transmits those wave lengths in the range of 315 to 400 millimicrons so as to obtain a desirable suntan.

Heretofore a number of formulations have been proposed for this purpose. For the most part, they are based on aromatic compounds exhibiting an absorption in the UV in the zone between 280 and 315 millimicrons and, more particularly, between 295 and 305 millimicrons.

In addition to this absorbing power, such compounds must have other properties and in particular they must not absorb the wave lengths of light in the zone ranging from 315 to 400 millimicrons, they should be non-volatile and they should also be resistant to both fresh and salt water and to perspiration. Additionally they should exhibit cosmetic compatibility with other components which may be present in suntan formulations and they should be non-odorous, non-toxic and non-irritating, i.e. entirely harmless to the user.

Among these characteristics, non-toxicity and dermotological compatibility are of great importance.

Representative aromatic compounds which have heretofore been employed in suntan preparations include derivatives of para-aminobenzoic acid, derivatives of anthranilic acid, derivatives of cinnamic acid and dihydroxy and trihydroxy cinnamic acid, derivatives of coumarin and the like.

The rather current widespread use of such compounds as an "anti-solar filter", is not without certain disadvantages. Certain of these substances do not exhibit sufficient efficiency in their ability to absorb the wave lengths of light in the erythematous zone. Moreover many do not possess the requisite solubility characteristics necessary so as to be utilized in many different types of formulation, and finally, because of their low molecular weight, many are able to penetrate through the epidermis of the skin into the human body which, in certain cases, can cause unfavorable side effects.

In an effort to remedy the inconveniences of these compounds, it has also been proposed to fix on macromolecular chains of certain copolymers, filters absorbing in UV in the erythematous region.

Among the polymers of this type described in the literature, one can in particular cite those resulting from the polymerization of 2-hydroxy (3-acryloxy or methacryloxy-2 hydroxy-4-propoxy) benzophenone with a comonomer of the methyl methacrylate type or of an unsaturated carboxylic acid such as acrylic, methacrylic, itaconic or crotonic acid, or the like.

However, these copolymers have not been found to be fully effective in cosmetic compositions because often they are quite difficult to formulate with other components generally found in a wide variety of anti-solar compositions and often they absorb only a portion of the undesirable wave lengths in the erythematous zone.

In effect, the nature of the function which permits the linking of the filter moiety to the polymeric chain of these known materials seriously limits the number of aromatic residues which impart the filtering or absorping characteristics to the polymer and thus it has been found that there is often not a sufficient amount of such aromatic residues to provide the degree of efficacy desired or required.

To overcome these disadvantages, the applicants have now provided anti-solar polymers wherein the residue which imparts to the polymer the ability to absorb wave lengths in the erythematous zone is linked to the polymeric chain by an intermediate chemical function of a particular type.

Thus, the present invention relates to an anti-solar polymer which contains in the macromolecular chain thereof at least one unit having the formula ##STR1## wherein F is a residue derived from an aromatic compound imparting to the polymer the ability to absorb those wave lengths of light in the range of about 280 and 315 millimicrons.

It has been observed that the use of the anti-solar polymers of the present invention in cosmetic compositions is highly advantageous since the linking of the aromatic residue to the macromolecular chain avoids or at least significantly retards the migration of an otherwise non-linked absorbent moiety through the skin into the human body thereby avoiding an undesirable side effects which have been experienced in the use of heretofore known anti-solar filters.

The importance of this feature can be easily appreciated especially since repeated applications of the anti-solar compositions of this invention are generally not necessary to achieve the desired results which thereby avoids any substantial risk of a massive absorption of the filter compounds into the body.

The anti-solar polymers of this invention generally have an average molecular weight generally between 2000 and 1,000,000 and the radical represented by F can be derived from a variety of aromatic compounds. Representative radicals include aryl, alkyl aryl, alkenylaryl, each of which can optionally be substituted, as well as aromatic heterocyclic radicals, also optionally substituted.

In particular the radical F can be selected from the group consisting of: ##SPC1##

wherein R is selected from the group consisting of hydrogen and CH₃ and R₁ is selected from the group consisting of CH₃ and OCH₃ ##SPC2## ##SPC3##

Because of the variety of the nature of the aromatic radicals that can be linked to the polymer chain, it is possible to fully cover the erythematous zone simply by a judicious selection of the appropriate aromatic compound to be linked to said polymer chain.

The anti-solar polymers of the present invention can be either homopolymers or copolymers.

Thus, in the homopolymers of this invention, in the repeating unit defined by formula I, the values of F are the same whereas in the copolymers of this invention, in the said repeating unit, the values of F are different.

The ability to obtain copolymers having fixed on their macromolecular chains aromatic radicals of differing structures is a highly desirable feature since by choosing the appropriate aromatic compounds, it is thus possible to provide a single copolymer which can cover the entire erythematous zone, thereby producing an anti-solar filter of great efficacy.

The polymers of the invention can also be bipolymers, terpolymers or the like, and they can include, at the same time, units of formula I wherein F is the same or different, and one or more other units can be derived from ethylenically unsaturated monomers.

The selection of the ethylenically unsaturated monomers or comonomers for use in the production of the polymers of the present invention is generally dependent on the function of the desired use of the resulting composition or, more exactly, on the type of formulation that is desired.

Thus it is possible to impart to the anti-solar polymers of this invention different characteristics by varying the nature of the comonomer used.

Representative comonomers include:

a. N-vinylpyrrolidone,

b. N-methacryloyl D-glucosamine,

c. dimethylaminoethyl methacrylate

d. stearyl methacrylic

e. stearyl acrylate and

f. methyl methacrylate

The first three of these comonomers generally increase the solubility of the resulting polymer in aqueous solutions while the last three ordinarily increase the solubility of the polymer in oil.

Copolymers of the present invention can have the formula ##STR2## wherein F has the meaning given above, R¹ represents hydrogen or methyl and

Y represents a radical selected from the group consisting of ##SPC4##

(ii). ##STR3## wherein X represents D-glucosamine, dimethylamino ethyl optionally quaternized and C₁₈ H₃₇.

The amount of the comonomer present in the anti-solar polymer of the present invention is variable but it is generally between about 20 and 90% of the total weight of the polymer.

This latter content, as can be seen, can vary rather widely and the particular content selected can depend, for instance, on the particular use chosen for the resulting polymer.

Also, the anti-solar polymers of this invention are characterized in that the weight of the repeating unit is generally between about 10-100% of the total weight of the polymer.

The present invention also relates to a process for preparing the said anti-solar polymers.

This process comprises preparing in a first stage a monomer, designated a "solar-filter monomer", of the formula ##STR4## wherein F has the same meaning given above, this said monomer in a second stage then being homopolymerized or copolymerized with one or more other comonomers.

The "solar-filter monomer" is prepared in a conventional manner by reacting, cold, in a sulfuric acid medium N-methylate acrylamide on the aromatic compound F. The time of the reaction is generally in the order of 10 hours to 4 days and is effected ordinarily at about ambient temperature.

The polymerization reaction can be effected according to conventional polymerization reactions, i.e., in mass, in solution, in suspension or in emulsion.

The polymerization initiators utilized are generally conventional free radical polymerization initiators and the choice of any one particular initiator can depend principally on the different monomers used as well as on the nature of reaction medium selected.

Representative usable initiators include the peroxides, such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, tertiobutyl hydroperoxide or benzoyl hydroperoxide, a catalyst which by decomposition liberates an inert gas, such as azobisisobutyonitrile, an oxidation-reduction catalyst such as sodium persulfate, sodium sulfite and H₂ O₂. The concentration of the initiator is generally between about 0.2 - 35 weight percent, preferably between 0.5 - 20 weight percent, of the total weight of the monomer content.

The molecular weight of the anti-solar polymers of the present invention can be regulated by introducing, during the course of polymerization reaction, small amounts, i.e. about 0.05 - 0.15 weight percent of a chain regulating agent such as an aldehyde, for instance, butyraldehyde or a halogenated substance such as chloroform, bromoform, carbon tetrachloride, and the like.

At the end of the polymerization reaction, the polymer obtained can, if desired, be purified by, for example, treating it with an ion exchange resin.

The present invention also relates to an anti-solar cosmetic composition containing as the active component for absorbing wave length of light in the range of 280 to 315 millimicrons at least one anti-solar polymer as described above.

These cosmetic compositions can be present in diverse forms, the choice of any particular form being dependent upon the desired use of the composition. Preferably, these compositions are present in the form of an aqueous emulsion, lotion, cream, milk, gel or in the form of an aerosol. These compositions can also be present in the form of an aqueous or hydroalcoholic (ethanol or isopropanol) solution or even in the form of an oily solution.

When the compositions of the present invention are present in the form of an aerosol, they are packaged under pressure in a conventional aerosol bomb or container in the presence of a propellant gas which is preferably a halogenated hydrocarbon or a mixture of said hydrocarbons, such as, for example, mixtures of trichlorofluoromethane and dichlorodifluoromethane.

In these cosmetic compositions, the concentration of the polymers described above can be varied for any particular concentration can depend on the degree of protection desired. However, the concentration of the anti-solar polymer in these compositions is generally between about 0.2 - 20% by weight of the total composition.

These anti-solar cosmetic compositions can also contain conventional cosmetic adjuvants such as fatty bodies (oils, fats and waxes), emulsifying agents, surfactants, perfumes, silicone oils, pigments, dyes or preservatives.

The incorporation into these compositions of colored pigments also permits coloring the skin and masking skin flaws.

By applying to the skin the composition of the present invention, there is formed a film exhibiting good affinity vis-a-vis the epidermis, thus assuring excellent protection against wave lengths of eight in the erythematous zone.

The present anti-solar polymers have been found to be non-toxic and their excellent protective action is 2-3 times greater than achieved by the same aromatic compound but which is not fixed to a polymer.

In addition to this protective action of the skin vis-a-vis solar rays, the polymers of the present invention can also be used to protect, against degradation, dyes contained in various cosmetic formulations such as for example a hair dye composition, a hair tinting composition and the like.

The following examples are given to illustrate the present invention.

EXAMPLE 1

Preparation of acrylamino methyl-4-hydroxy-benzo phenone of the formula ##SPC5##

Into a 500 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, and containing 19.8g of benzophenone in solution in 70g of sulfuric acid, there are introduced, in portions, 10 grams of N-methylal acrylamide while cooling the same.

The resulting mixture is thoroughly admixed by vigorously stirring the same and a light yellow solid forms. Agitation of the mixture is continued for 36 hours, then the solution is left to stand at rest for 48 hours at ambient temperature.

The mixture is then precipitated in a mixture of water and ice; the resulting precipitate being filtered, washed and taken up in ether.

The organic layers are washed with water until neutrality is reached. The ether phase is then dried with the ether being evaporated and the residue then dried under reduced pressure.

After two recrystallization in acetone, 20 grams of pure product are obtained.

    ______________________________________                                         Melting point                                                                             = 159°C                                                      EtOH                                                                                      = 236 millimicrons                                                                             Ksp = 62,000                                        λmax.sub.1                                                              EtOH                                                                                      = 296 millimicrons                                                                              Ksp = 50,000                                       λmax.sub.2                                                              ______________________________________                                    

EXAMPLE 2

Preparation of a copolymer of acrylamido methyl-4-hydroxy benzophenone/stearyl methacrylate

Into a 50 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 1g of acrylamino methyl 4-hydroxy benzophenone, 1.5g of stearyl methacrylate and 0.25g of azobis-isobutyronitrile in solution in 5 ml of acetone. The resulting mixture is heated for 8 hours at 80°C.

The mixture is then diluted with acetone and the polymer is precipitated in methanol, yielding 1.6g of pure polymer.

    ______________________________________                                         Hexane                                                                                = 295 millimicrons Ksp = 12,900                                         λmax                                                                    ______________________________________                                    

EXAMPLE 3

The preparation of acrylamido methyl-4-methoxy-2-hydroxy benzophenone of the formula ##SPC6##

Into a 250 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, and containing 22.8 g of 4-methoxy-2-hydroxy benzophenone in solution in 60g of sulfuric acid cooled by ice. There are introduced, in portions, 10g of N-methylol acrylamide. The resulting solution is left to stand, with agitation, for 24 hours, after which it is left to stand, at rest, for 2 days at ambient temperature.

The mixture is then poured over ice thereby producing a light brown precipitate which is filtered, washed with water and ethyl acetate. After drying, the resulting product is recrystallized in isopropanol.

    ______________________________________                                         Melting Point = 194°C                                                   CHCl.sub.3                                                                              = 293 millimicrons                                                                                Ksp = 52,200                                       λmax                                                                    ______________________________________                                    

EXAMPLE 4

Preparation of a copolymer of acrylamido methyl-4-methoxy-2-hydroxy benzophenone/stearyl methacrylate.

Into a 50 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 2.5g of acrylamido methyl-4-methoxy-2-hydroxy benzophenone, 2.5g of stearyl methacrylate and 0.2g of azobis-isobutyronitrile in solution in 10g of acetone.

The resulting mixture is heated for 8 hours at 80°C, then diluted with benzene and finally precipitated in methanol, yielding 1.9 g of pure polymer.

    ______________________________________                                         EtOH                                                                                   = 287 millimicrons Ksp = 10,600                                        λmax                                                                    ______________________________________                                    

EXAMPLE 5

Preparation of 3-(acrylamido methyl benzylidene) DL camphor of the formula ##SPC7##

Into a one liter reactor provided with a mechanical agitator, a condenser and a calcium chloride guard, there are dissolved 120g of benzylidene D.L. camphor in 240 g of pure sulfuric acid.

Thereafter, there is introduced into the resulting solution 1 g of sodium nitrite and the mixture is cooled with an ice bath.

When the interior temperature reaches 0°C there are then introduced over a one hour period 56g of N-methylol acrylamide. The resulting mixture is left to stand at ambient temperature while being stirred for 48 hours.

The resulting thick brown solution is then slowly poured into a mixture of 500g of ice and 500 g of water with vigorous agitation.

A light beige precipitate forms which is recovered and washed with water and then put into solution in 500 ml of ethyl acetate.

The organic layers are washed with water until the wash waters are neutral at which time they are dried on anhydrous sodium sulfate.

After filtering and evaporation of the solvent, the product is dried under reduced pressure, thus yielding 60g of an oil which crystallizes on cooling. The crude product is then washed with 90 ml of sulfuric ether and the solid residue is then filtered and dried, yielding 31g which are recrystallized in carbon tetrachloride (28g).

    ______________________________________                                         Melting point = 134°C                                                   CHCl.sub.3                                                                              = 295 millimicrons                                                                                Ksp = 80,000                                       λmax                                                                    ______________________________________                                    

EXAMPLE 6

Preparation of a homopolymer of 3-(acrylamido methyl benzylidene) D.L. camphor.

Into a 25 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 4g of crude 3-(acrylamido methyl benzylidene) D.L. camphor, obtained in the manner set forth in Example 5, and 0.4g. of azobis-isobutyronitrile dissolved in 4 ml of methanol. The resulting mixture is heated for 24 hours at the reflux of methanol and, after cooling, the precipitated polymer is dissolved in chloroform.

This solution is then poured into methanol and the precipitated polymer is filtered and dried under reduced pressure, yielding 2.5g of pure product.

    ______________________________________                                         CHCl.sub.3                                                                              = 296 millimicrons                                                                                Ksp = 52,000                                       λmax                                                                    ______________________________________                                    

EXAMPLE 7

Preparation of a copolymer of 3-(acrylamido methyl benzylidene) D.L. camphor/stearyl methacrylate.

Into a 100 ml flask, provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 15g of pure 3-(acrylamido methyl benzylidene) D.L. camphor, 15g of stearyl methacrylate, 3g of azobis-isobutyronitrile and 60g of acetone. The resulting solution is heated, with agitation, for 24 hours at 80°C and the polymer precipitates on cooling. After filtering the polymer therefrom, it is dissolved in heptane and precipitated in 2 liters of absolute ethanol, yielding 15g of pure product.

    ______________________________________                                         Heptane                                                                                 = 291 millimicrons                                                                               Ksp = 20,000                                        λmax                                                                    ______________________________________                                    

EXAMPLE 8

Preparation of a copolymer of 3-(acrylamido methyl benzylidene) D.L. camphor/dimethylamino ethyl methacrylate quaternized with dimethyl sulfate.

Into a 250 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 15g of 3-(acrylamido methyl benzylidene) D.L. camphor, 5g of dimethylaminoethyl methacrylate, 2g of azobis-isobutyronitride and 40g of dioxane.

The resulting solution is agitated for 24 hours at 80°C after which there are introduced 5g of dimethyl sulfate in solution in 20g of methanol.

The temperature of the resulting mixture is held for 4 hours at 80°C at which time the polymer is precipitated in 2 liters of ethyl acetate, yielding 17g of pure polymer.

    ______________________________________                                         EtOH + H.sub.2 O                                                                         = 295 millimicrons                                                                               Ksp = 25,500                                       λmax                                                                    ______________________________________                                    

EXAMPLEE 9

Preparation of a copolymer of 3-(acrylamido methyl benzylidene) D.L. camphor/methylmethacrylate/dimethylaminoethyl methacrylate quaternized with dimethyl sulfate.

Into a 100 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 8g of 3-(acrylamido methyl benzylidene) D.L. camphor, 8 g of methyl methacrylate, 8g of dimethylaminoethyl methacrylate, 0.24g of azobis-isobutyronitrile and 24g of absolute ethanol.

The resulting solution is held at a temperature of 80°C for 10 hours with agitation at which time there are introduced 5g of dimethyl sulfate in solution in 25 ml of methanol. The temperature of the solution is held for four additional hours at 80°C. Thereafter, the polymer is precipitated in ethyl acetate, yielding 22g of pure product.

    ______________________________________                                         EtOH + H.sub.2 O                                                                         = 295 millimicrons                                                                               Ksp = 8,500                                        λmax                                                                    ______________________________________                                    

EXAMPLE 10

Preparation of a copolymer of 3-(acrylamido methyl benzylidene) D.L. camphor/N-vinyl pyrrolidone.

Into a 25 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 0.5 g of 3-(acrylamido methyl benzylidene) D.L. camphor, 2g of N-vinylpyrrolidone, 0.15g of azobis-isobutyronitrile and 3g of ethanol.

The resulting mixture is heated for 8 hours at 80°C and the polymer is precipitated in an 8:1 mixture of sulfuric ether and isopropanol, yielding 1.5 g of pure polymer.

    ______________________________________                                         EtOH + H.sub.2 O                                                                         = 298 millimicrons                                                                               Ksp = 18,100                                       λmax                                                                    ______________________________________                                    

EXAMPLE 11

Preparation of a copolymer of 3-(acrylamido methyl benzylidene) D.L. camphor/methylacrylate/dimethylaminoethyl methacrylate quaternized with dimethyl sulfate.

Into a 250 ml flask provided with an agitator, a condenser and a nitrogen lead in tube, there are introduced 12g of 3-(acrylamido methyl benzylidene) D.L. camphor, 8g of dimethylaminoethyl methacrylate, 8g of methyl acrylate, 0.3 g of azobis-isobutyronitrile and 28g of absolute ethanol.

The resulting solution is heated for 8 hours at 80°C and, after cooling, there are introduced 7g of dimethyl sulfate in solution in 28g of methanol. The resulting solution is heated for 24 hours at 80°C.

The polymer is precipitated in a 50:50 mixture of ethylacetate and dioxane, yielding 24g of pure polymer.

    ______________________________________                                         EtOH + H.sub.2 O                                                                         = 295 millimicrons                                                                               Ksp = 17,800                                       λmax                                                                    ______________________________________                                    

EXAMPLE 12

Preparation of a copolymer of 3-(acrylamido methyl benzylidene) D.L. camphor/N-methacryloyl D-glucosamine.

In a 50 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are dissolved 5g of N-methacryloyl D glucosamine, 5g of 3-(acrylamido methyl benzylidene) D.L. camphor and 0.5 g of azobis-isobutyronitrile in 30g of dimethylformamide.

The resulting solution is heated for 24 hours at 80°C. The polymer is then precipitated in water, cooled in a 50:50 mixture of ethanol and methanol and precipitated in an 8:1 mixture of sulfuric ether and isopropanol, yielding 6g of pure polymer

    ______________________________________                                         EtOH + H.sub.2 O                                                                         = 297 millimicrons                                                                               Ksp = 24,200                                       λmax                                                                    ______________________________________                                    

EXAMPLE 13

Preparation of a copolymer of 3-(acrylamido methyl benzylidene) D.L. camphor/stearyl acrylate.

Into a 10 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 1.6g of 3-(acrylamido methyl benzylidene) D.L. camphor, 0.6g of stearyl acrylate and 0.2 g of azobis-isobutyronitrile in solution in 3g of acetone.

The resulting solution is heated to reflux for 18 hours at which time the polymer is precipitated in 250 ml of methanol, yielding 018g of pure polymer.

    ______________________________________                                         CHCl.sub.3                                                                              = 295 millimicrons                                                                                Ksp = 51,100                                       λmax                                                                    ______________________________________                                    

EXAMPLE 14

Preparation of a copolymer of 3-(acrylamido methyl benzylidene) D.L. camphor/stearyl methacrylate/methyl acrylate.

Into a 10 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 1.2g of 3-(acrylamido methyl benzylidene) D.L. camphor, 0.6g of stearyl methacrylate, 0.2g of methyl acrylate and 0.2g of azobis-isobutyronitrile in 3g of acetone.

The resulting solution is held at a temperature of 80°C for 18 hours at which time it is diluted with 10 ml of heptane and poured into 500 ml of methanol to precipitate the polymer, yielding 1.3g of the pure polymer.

    ______________________________________                                         CHCl.sub.3                                                                              = 295 millimicrons                                                                                Ksp = 36,500                                       λmax                                                                    ______________________________________                                    

EXAMPLE 16

Preparation of acrylamido methyl-7-hydroxy-4-methyl coumarin of the formula ##SPC8##

Into a 250 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, and containing 17.6g of 7-hydroxy-4-methyl coumarin and 60g of pure sulfuric acid cooled in ice, there are introduced 10g of N-methylol acrylamide.

The resulting mixture is agitated for 2 days at ambient temperature and then left to stand at rest for an addtional 2 days.

The solution is then poured into ice and the resulting precipitate is taken up in ethylacetate, washed with water and dried under reduced pressure. After recrystallizing the precipitate in ethanol there are obtained 10g of pure product.

    ______________________________________                                         CHCl.sub.3                                                                              = 323 millimicrons                                                    λmax                                                                    ______________________________________                                    

EXAMPLE 17

Preparation of a copolymer of acrylamido methyl-7-hydroxy-4-methyl coumarin/stearyl methacrylate.

Into a 50 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 1g of acrylamido methyl 7-hydroxy-4-methyl coumarin, 2g of stearyl methacrylate, 0.3g of azobis-isobutyronitrile and 6g of dimethylformamide.

The resulting mixture is heated for 8 hours at 80°C at which time it is diluted with benzene and the polymer is then precipitated in methanol, yielding 1.2g of pure polymer.

    ______________________________________                                         Hexane                                                                                 = 324 millimicrons Ksp = 6,300                                         λmax                                                                    ______________________________________                                    

EXAMPLE 18

Preparation of 3-(acrylamidomethyl)4-hydroxy coumarin of the formula ##SPC9##

In a 250 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are dissolved 16.2 g of 4-hydroxy coumarin in 50g of pure sulfuric acid. The reaction is exothermic and the temperature reaches 80°C. After cooling to 0°C by a mixture of ice and salt, 11g of N-methylol acrylamide are slowly added thereto.

The resulting mixture is then left to stand with agitation until its temperature returns to ambient temperature. Agitation of the same is then continued for an additional 4 days, at which time the solution is poured into a mixture of ice and water to precipitate the polymer in the form of a beige powder which is filtered, washed with water, dried under reduced pressure and recrystallized in ethanol, yielding 15g of the polymer, having a melting point of 194°C.

    ______________________________________                                         EtOH + H.sub.2 O                                                                          = 288 millimicrons                                                                              Ksp = 48,00                                        λmax                                                                    EtOH + H.sub.2 O                                                                          = 304 millimicrons                                                                              Ksp = 50,000                                       λmax                                                                    ______________________________________                                    

EXAMPLE 19

Preparation of a homopolymer of 3-(acrylamido methyl)-4-hydroxy coumarin.

Into a 50 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 2.5 g of 3-(acrylamido methyl)-4-hydroxy coumarin and 0.25g of azobisisobutyronitrile in 15 ml of dimethylformamide.

The resulting mixture is heated for 24 hours at 100°C at which time the homopolymer is precipitated in lukewarm dichloromethane, yielding 0.6g of product.

    ______________________________________                                         MeOCH.sub.2 CH.sub.2 OH                                                                   = 310 millimicrons                                                                            Ksp = 14,200.                                        λmax                                                                    ______________________________________                                    

EXAMPLE 20

Preparation of a copolymer of 3-(acrylamido methyl)-4-hydroxy coumarin/N-vinyl pyrrolidone.

Into a 50 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 3g of 3-(acrylamido methyl)-4-hydroxy coumarin, 7g of N-vinyl pyrrolidone, 0.5g of azobis-isobutyronitrile and 10g of dimethylformamide.

The resulting solution is agitated for 24 hours at 100°C at which time it is poured into sulfuric ether thereby precipitating the polymer.

The solution is filtered and this recovered precipitate is dissolved in methanol and cooled in nitromethane, thus yielding 3g of pure polymer.

    ______________________________________                                         EtOH                                                                                   = 282 millimicrons Ksp = 4,540                                         λmax                                                                    EtOH                                                                                   = 305 millimicrons Ksp = 4,200                                         λmax                                                                    ______________________________________                                    

EXAMPLE 21

Preparation of a copolymer of 3-(acrylamido methyl)-4-hydroxy coumarin/dimethylaminoethyl methacrylate quaternized with dimethyl sulfate.

Into a 50 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 7g of 3-(acrylamido methyl)-4-hydroxy coumarin, 3g of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate, 1g of azobis-isobutyronitrile and 30g of dimethylformamide.

The resulting mixture is heated for 24 hours at 100°C at which time it is poured into lukewarm dichloromethane to precipitate the polymer which is then filtered therefrom and dried, yielding 5g of pure polymer.

    ______________________________________                                         H.sub.2 O                                                                               = 302 millimicrons                                                                               Ksp = 12,200                                        λmax 1                                                                  H.sub.2 O                                                                               = 290 millimicrons                                                                               Ksp = 11,900                                        λmax                                                                    ______________________________________                                    

EXAMPLE 22

Preparation of a copolymer of stearylacrylate/3-(acrylamido methyl)-4-hydroxy coumarin/acrylamido methyl-4-hydroxy benzophenone/3-(acrylamido methyl benzylidene) D.L. camphor.

Into a 50 ml flask provided with a condenser, a nitrogen lead in tube and an agitator, there are introduced 2g of 3-(acrylamido methyl)-4-hydroxy coumarin, 1g of acrylamido methyl-4-hydroxy benzophenone, 0.5g of 3-(acrylamido methyl benzylidene) D.L. camphor, 3.5g of stearylacrylate, 0.7g of azobis-isobutyronitrile and 15g of dimethylformamide.

The resulting mixture is heated, with agitation, at 80°C for 24 hours at which time it is diluted with chloroform, filtered and then precipitated in 800 ml of lukewarm acetone.

The resulting polymer which precipitates is filtered therefrom, washed and dried under a reduced pressure, yielding 4.1g of pure polymer.

    ______________________________________                                         CHCl.sub.3                                                                               = 280 millimicrons                                                                               Ksp = 20,000                                       λmax 1                                                                  CH.sub.3 Cl.sub.3                                                                        = 298 millimicrons                                                                               Ksp = 17,500                                       λmax 2                                                                  ______________________________________                                    

EXAMPLES OF COSMETIC COMPOSITIONS EXAMPLES 23-27

An anti-solar oil composition in accordance with the present invention is prepared by admixing the following components:

    ______________________________________                                         Polymer of Example 2    10g                                                    Perfume                 0.5g                                                   Hydroxybutyltoluene     0.0625g                                                Vaseline oil, q.s.p.   100 g                                                   ______________________________________                                    

The above anti-solar oil composition is repeated except that the polymer of Example 2 is replaced by the same quantity of the polymer prepared in accordance with each of Examples 4, 7, 17 and 22. A comparably effective anti-solar oil composition results in each instance.

EXAMPLES 28-31

An anti-solar lotion in accordance with the present invention is prepared by admixing the following components:

    ______________________________________                                         Polymer of Example 13     5g                                                   Lanolin                   2.5g                                                 Hydroxybutylanisole                                                             (antioxidant)            0.0625                                               Triglycerides of octanoic and                                                   decanoic acids           40g                                                  Ethyl alcohol (96%).q.s.p.                                                                              100g                                                  ______________________________________                                    

The above anti-solar lotion is repeated except that the polymer of Example 13 is replaced by the same quantity of the polymer prepared in accordance with each of Examples 14, 15 and 22. A comparably effective anti-solar lotion results in each instance.

EXAMPLES 32 - 33

An anti-solar aerosol composition in accordance with the present invention is prepared by admixing the following components:

    ______________________________________                                         Polymer of Example 13     5g                                                   Absolute ethyl alcohol    30g                                                  Isopropyl palmitate       20g                                                  Ricin oil                 2g                                                   Lanolin                   2g                                                   Perfume                   1g                                                   Dichlorodifluoromethane   40g                                                   (propellant)                                                                  ______________________________________                                    

The above aerosol composition is packaged under pressure in a conventional aerosol container.

Further, the above aerosol composition is repeated except that the polymer of Example 13 is replaced by the same quantity of the polymer prepared in accordance with Example 22. A comparably effective anti-solar aerosol formulation results.

EXAMPLES 34 - 36

An anti-solar aerosol foam composition in accordance with the present invention is prepared by admixing the following components:

    ______________________________________                                         Polymer of Example 4    10g                                                    Stearic acid            0.5 g                                                  Lauric acid             0.5g                                                   Palmitic acid           2.5g                                                   Vaseline oil            45.7g                                                  Ethyl p-hydroxybenzoate 0.3g                                                   Triethanolamine         1.5g                                                   Reliculated polyacrylic acid                                                    sold under the tradename                                                       CARBOPOL (0.5% solution in                                                     H.sub.2 O)-carboxy-polymethylene                                                                      38.5g                                                  Perfume                 0.5g                                                   ______________________________________                                    

85g of the above composition are packaged under pressure in a conventional aerosol container or bomb together with 13g of dichlorodifluoromethane.

The above aerosol formulation is repeated except that the polymer of Example 4 is replaced by the same quantity of the polymer prepared in accordance with each of Examples 7 and 17. A comparably effective anti-solar aerosol foam results in each instance.

EXAMPLES 37 - 38

An anti-solar cream is prepared in accordance with the present invention by admixing the following components:

    ______________________________________                                         Polymer of Example 15   10g                                                    Triglycerides of octanoic and                                                   decanoic acids         31g                                                    Glycerol monostearate   6g                                                     Polyethylene glycol stearate                                                                           2g                                                     Stearic acid            2g                                                     Cetyl alcohol           1.2g                                                   Lanolin                 4g                                                     Silicone oil            1g                                                     Methyl p-hydroxybenzoate                                                                               0.3g                                                   Propylene glycol        2g                                                     Triethanolamine         0.1g                                                   Perfume                 0.5g                                                   Water, q.s.p.           100g                                                   ______________________________________                                    

The above anti-solar cream formulation is repeated except that the polymer of Example 15 is replaced by the same quantity of the polymer prepared in accordance with Example 14. A comparably effective anti-solar cream results.

EXAMPLE 39

An anti-solar milk is prepared in accordance with the present invention by admixing the following components:

    ______________________________________                                         Polymer of Example 2   5g                                                      Cetyl-stearyl alcohol  2g                                                      Cetyl alcohol          2g                                                      Vaseline oil           20g                                                     Lanolin                4g                                                      Stearic acid           0.5g                                                    Silicone oil           0.3g                                                    Propyl p-hydroxy benzoate                                                                             0.4g                                                    Glycerin               5g                                                      Reliculated polyacrylic acid                                                    sold under the tradename                                                       CARBOPOL (carboxypoly-                                                         methylene)            0.15g                                                   Triethanolamine        0.20g                                                   Perfume                0.3g                                                    Water,q.s.p.           100g                                                    ______________________________________                                    

EXAMPLES 40 - 44

An anti-solar cream formulation in accordance with the present invention is prepared by admixing the following components:

    ______________________________________                                         Polymer of Example 8    15g                                                    Cetyl-stearyl alcohol   2g                                                     Glycerol monostearate   4g                                                     Cetyl alcohol           4g                                                     Vaseline oil            5g                                                     Butyl stearate          5g                                                     Propylene glycol        7g                                                     Silicone oil            0.125g                                                 Nonionic polymer of high                                                        molecular weight sold under                                                    the tradename POLYOX (5%                                                       solution in water)     3.5g                                                   Methyl-p-hydroxy benzoate                                                                              0.3g                                                   Perfume                 0.4g                                                   Water, q.s.p.           100g                                                   ______________________________________                                    

The above anti-solar cream formulation is repeated except that the polymer of Example 8 is replaced by the same quantity of the polymer prepared in accordance with Examples 9, 10, 11 and 12. A comparably effective anti-solar cream results in each instance.

EXAMPLE 45

An anti-solar milk in accordance with the present invention is prepared by admixing the following components:

    ______________________________________                                         Polymer of Example 20   5g                                                     Polymer of Example 21   5g                                                     Sipol wax               5g                                                     Vaseline oil            6g                                                     Isopropyl myristate     3g                                                     Propyl p-hydroxy benzoate                                                                              0.3g                                                   Glycerin                20g                                                    Perfume                 0.3g                                                   Water, q.s.p.           100g                                                   ______________________________________                                    

EXAMPLE 46

An anti-solar aerosol foam composition in accordance with the present invention is prepared by admixing the following components:

    ______________________________________                                         Polymer of Example 10   10g                                                    Sipol wax               3.5g                                                   Vaseline oil            6g                                                     Isopropyl myristate     3g                                                     Methyl-p-hydroxybenzoate                                                                               0.3g                                                   Glycerin                10g                                                    Perfume                 0.3g                                                   Water, q.s.p.                                                                  ______________________________________                                    

87 g of the above composition are packaged in a conventional aerosol container together with 13g of dichlorodifluoromethane.

EXAMPLES 47 - 48

An anti-solar aerosol formulation in accordance with the present invention is prepared by admixing the following components.

    ______________________________________                                         Polymer of Example 6       5g                                                  Methylcellosolve           30g                                                 Isopropyl myristate        20g                                                 Ricin oil                  2g                                                  Lanolin                    2g                                                  Perfume                    1g                                                  Dichlorodifluoromethane                                                         (Propellant)              40g                                                 ______________________________________                                    

The above aerosol formulation is packaged under pressure in a conventional aerosol container.

Further, the above aerosol aerosol formulation is repeated except that the polymer of Example 6 is replaced by the same quantity of the polymer prepared in accordance with Example 19. A comparably effective anti-solar aerosol formulation results.

USE OF ANTI-SOLAR COPOLYMERS TO PROTECT DYES EXAMPLE 49

A hair-setting lotion for coloring hair is prepared in accordance with the present invention by admixing the following components:

    ______________________________________                                         Copolymer of Example 11                                                                              0.3g                                                     Copolymer of vinylpyrrolidone/                                                  viyl acetate, 70/30, M.W. = 40,000                                                                  2g                                                       Ethyl alcohol         50g                                                      Dye-CI Basic Violet 1                                                           (CI 42535)           0.002g                                                   Water,q.s.p.          100g                                                     ______________________________________                                    

EXAMPLE 50

A hair setting lotion for coloring hair is prepared in accordance with the present invention by admixing the following components:

    ______________________________________                                         Copolymer of Example 12                                                                              0.3g                                                     Copolymer of crotonic acid/vinyl                                                acetate,90/10, MW = 40,000                                                                          2g                                                       Ethyl alcohol         50g                                                      Triethanolamine, q.s.p.                                                                              pH7                                                      Dye-CI Basic Violet 3                                                           (CI 42555)           0.002g                                                   Dye-Basic Violet 1                                                              (CI 42535)           0.001g                                                   Water, q.s.p.         100g                                                     ______________________________________                                     

What is claimed is:
 1. Anti-solar polymer having in the macromolecular chain thereof from 10 to 100% by weight of units of the formula ##EQU2## wherein F represents ##SPC10##and from 90% to 0% by weight of units derived from an ethylenically unsaturated monomer, said anti-solar polymer having an average molecular weight between about 2,000 and 1,000,000.
 2. The polymer of claim 1 wherein the amount of ethylenically unsaturated monomer is about 20-90 percent of the total weight of the polymer.
 3. Anti-solar polymer having in the macromolecular chain thereof from 10 to 100% by weight of units of the formula ##STR5## wherein F represents ##SPC11##and from 90 to 0% by weight of units of the formula ##STR6## wherein R₁ is selected from the group consisting of hydrogen and methyl and Y is -CO-O-X wherein X is CH₃ or C₁₈ H₃₇, said anti-solar polymer having an average molecular weight between about 2,000 and 1,000,000.
 4. Anti-solar polymer which is a homopolymer having in the macromolecular chain thereof units of the formula ##SPC12##said anti-solar polymer having an average molecular weight between about 2,000 and 1,000,000.
 5. Anti-solar polymer having in the macromolecular chain thereofa. units of the formula ##SPC13## b. units of the formula ##SPC14##wherein R'₁ is CH₃ or OCH₃ and R'₂ is OH or OCH₃, or R'₁ is OH and R'₂ is H, said units (a) and (b) representing from 10 to 100% of the total weight of the polymer, and c. from 90 to 0% by weight of units of the formula ##STR7## wherein R₁ is selected from the group consisting of hydrogen and methyl and Y is --CO--O--X wherein X is CH₃ or C₁₈ H₃₇, said anti-solar polymer having an average molecular weight between about 2,000 and 1,000,000.
 6. The polymer of claim 5 wherein R'₁ is OH and R'₂ is H.
 7. Anti-solar polymer having in the macromolecular chain thereofa. units of the formula ##SPC15## b. units of the formula ##SPC16##wherein R'₃, R'₄ and R'.sub. 5 are selected from the combinations consisting of i. R'₃ is OH, R'₄ is OCH₃ and R'₅ is H, ii. R'₃ is OH, R'₄ is H and R'₅ is C₆ H₅ and iii. R'₃ is H, R'₄ is OH and R'₅ is H, said units (a) and (b) representing from 10 to 100% of the total weight of the polymer, and c. from 90 to 0% by weight of units of the formula ##STR8## wherein R₁ is selected from the group consisting of hydrogen and methyl and y is --CO--O--X wherein X is CH₃ or C₁₈ H₃₇, said anti-solar polymer having an average molecular weight between about 2,000 and 1,000,000.
 8. Anti-solar polymer having in the macromolecular chain thereofa. units of the formula ##SPC17## b. units of the formula ##SPC18##wherein R'₁ is CH₃ or OCH₃ and R'₂ is OH or OCH₃ or R'₁ is OH and R'₂ is H, c. units of the formula ##SPC19##wherein R'₃, R'₄ and R'₅ are selected from the combinations consisting of i. R'₃ is OH, R'₄ is OCH₃ and R'₅ is H, ii. R'₃ is OH, R'₄ is H and R'₅ is C₆ H₅ and iii. R'₃ is H, R'₄ is OH and R'₅ is H, said units (a), (b) and (c) representing from 10 to 100% of the total weight of the polymer, and d. from 90 to 0% by weight of units of the formula ##STR9## wherein R₁ is selected from the group consisting of hydrogen and methyl and Y is --CO--O--X wherein X is CH₃ or C₁₈ H₃₇, said anti-solar polymer having an average molecular weight between about 2,000 and 1,000,000.
 9. The polymer of claim 8, wherein R'₃ is H, R'₄ is OH and R'₅ is H.
 10. The polymer of claim 9 which is a copolymer of stearyl acrylate/3-(acrylamidomethyl)-4-hydroxy coumarin/acrylamido methyl-4-hydroxy benzophenone/3-(acrylamidomethyl benzylidene( DL camphor. 